Copper-catalyzed C(sp)-H aryl amination enables modular synthesis of quinolines and 2-quinolinones  

作　　者：Yang Gao Haixia Li Simin Yang Yanping Huo Qian Chen Xianwei Li Zhe Wang Xiao-Qiang Hu 

机构地区：[1]School of Chemical Engineering and Light Industry,Guangdong University of Technology,Guangzhou,510006,China [2]Jieyang Branch of Chemistry and Chemical Engineering Guangdong Laboratory,Jieyang,515200,China [3]Key Laboratory of Catalysis and Energy Materials Chemistry of Ministry of Education&Hubei Key Laboratory of Catalysis and Materials Science,School of Chemistry and Materials Science,South-Central University for Nationalities,Wuhan,430074,China

出　　处：《Science China Chemistry》2024年第2期595-603,共9页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China (22271065,22271314);the Guangzhou Basic and Applied Research (202201010396)。

摘　　要：Herein,we disclose a novel copper-catalyzed C(sp)-H aryl amination of terminal alkynes with anthranils,enabling the rapid generation of highly reactive secondary N-aryl ynamines for the modular synthesis of structurally diverse C2-substituted quinolines and 2-quinolinones.The in-situ formed carbonyl-ynamines are prone to tautomerize to carbonyl-ketenimines,which can efficiently react with a series of nucleophiles,including amines,alcohols,phenols,thiols,thiophenols,active-methylene compounds,and even water to produce various quinoline derivatives with the generation of H_(2)O as a sole and green byproduct.This method also unlocks a practical route to create various quinoline-fused heterocycles and can be successfully applied to the late-stage modification of complex molecules and the concise synthesis of bioactive targets.Mechanistic studies reveal a coppercatalyzed inner-sphere nitrene transfer process by using anthranils as novel aryl nitrene precursors.

关 键 词：copper catalysis anthranils C(sp)-H aryl amination carbonyl-ketenimines QUINOLINES 

分 类 号：O626[理学—有机化学] O621.251[理学—化学]